EP2430112B1 - Materialien und verfahren zur herstellung von nanoverbundstoffen - Google Patents

Materialien und verfahren zur herstellung von nanoverbundstoffen Download PDF

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EP2430112B1
EP2430112B1 EP10767840.1A EP10767840A EP2430112B1 EP 2430112 B1 EP2430112 B1 EP 2430112B1 EP 10767840 A EP10767840 A EP 10767840A EP 2430112 B1 EP2430112 B1 EP 2430112B1
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cdse
colloidal
sns
fept
capping agent
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EP2430112A2 (de
EP2430112A4 (de
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Dmitri V. Talapin
Maksym V. Kovalenko
Jong-Soo Lee
Chengyang Jiang
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University of Chicago
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Definitions

  • the disclosure generally relates to materials and methods for the preparation of nanocomposites. More specifically, the disclosure relates to inorganic capped colloidal materials and the methods of depositing these inorganic capped colloidal materials on a substrate to form nanocomposites. Still more specifically, the disclosure relates to the selective deposition and formation of nanocomposites on a substrate.
  • Nanoscale materials materials with at least one dimension between about 1 and 1000 nm, have increasingly garnered attention due to their potential electronic, photophysical, chemical, and medicinal effects.
  • the large-scale industrial application of nanoscale materials has generally focused on the formation of nanometer thick films and/or nanometer wide wires.
  • Many of these industrially-applied nanoscale materials display extraordinary electronic and photophysical properties, but more often the materials lack the features that originally drew scientific interest toward nanocrystals, nanorods, and nanowires.
  • nanocrystals, nanorods, and nanowires have led to the self-assembly of ordered nanoarrays.
  • These self-assembled ordered nanoarrays have been produced from stable colloidal solutions of nanomaterials.
  • close-packed nanocrystal films have been made by spin-coating or drop casting of colloidal solutions. Often these films show short range ordering, but forces such as entropy, electrostatics, and van der Waals interactions can cause these materials to self-assemble into superlattices.
  • These techniques have afforded binary superlattices with tunable electronic structures based on the colloidal materials employed in the synthesis.
  • a larger-scale approach to the synthesis of solid state materials encompassing nanocrystals is the impregnation and forced crystallization of nanocrystals from melts of inorganic materials.
  • This rapid quenching approach can provide nanocrystalline material in bulk inorganic phases but lacks any methodology for the formation of ordered nanoarrays in the bulk material.
  • nanocomposites of nanocrystals and conjugated polymers can yield tunable semiconducting photonic structures, and with unique optical, electrical, magnetic, electrochromic, and chemical properties. See for example U.S. Pat. No. 7,200,318 .
  • inorganic solids as the functional material.
  • One example of an applicable inorganic solid that incorporates nanoscale materials is the fabrication of inorganic nanocomposites described in U.S. Pat. 7,517,718 .
  • This methodology involves the codeposition of a nanocrystalline material with an inorganic matrix precursor from a homogeneous hydrazine solution, a technique similar to the deposition of nanocrystalline materials in polymers as described in J. W. Lee et al., Advanced Materials 2000, 12, 1102 .
  • This methodology fails to provide the selectivity of structure for the synthesis of tunable semiconducting materials, does not prevent the carbon contamination of the synthesized inorganic nanocomposite, and requires a highly toxic, hypergolic solvent.
  • Patent Applications 11/403090 ; 11/484785 ; 11/679746 ; 11/680047 ; 11/680344 ; 11 /683880 ; 11/687306 ; 11/747701 ; 11/752748 ; 11/863129 ; 11 /866974 ; 11/896549 ; 11/952783 ; 12/048061 ; 12/052380 ; and 12/350615 ; and the following International Patent Applications: PCT/2005/016481 ; PCT/2005/024131 ; PCT/2005/024211 ; PCT/2006/003652 ; PCT/2006/027124 ; PCT/2006/027125 ; PCT/2007/015851 ; PCT/2007/025235 ; PCT/2007/063788 ; PCT/2007/063788 ; PCT/2007/065951 ; PCT/2007/065951 ; PCT/2007/069572 ; PCT/
  • compositions and methods for making that composition having a nanoparticle capped with an inorganic capping agent Disclosed herein is a composition and a method for making that composition having a nanoparticle capped with an inorganic capping agent.
  • the method generally includes at least two immiscible solvents and the exchange of an organic capping agent on a nanoparticle with the herein described inorganic capping agent.
  • compositions made of the nanoparticle and the inorganic capping agent are isolable, can be purified, and importantly may display approximately the same opto-electronic characteristics as the nanoparticle with an organic capping agent.
  • compositions on a substrate.
  • the composition can be deposited as thin or bulk films by a variety of techniques with short or long range ordering of the nanoparticles.
  • the deposited composition importantly, displays approximately the same opto-electronic characteristics as the composition in solution.
  • Still another aspect of the disclosure is the thermal decomposition of the deposited composition to form inorganic matrices with imbedded nanoparticles.
  • the annealed composition has an inorganic matrix that corresponds to the thermal decomposition product of the inorganic capping agent. Additionally, as the annealed composition can be produced from the deposited composition with ordered nanoparticles (arrays), the annealed composition can have ordered arrays of nanoparticles in a solid state matrix. The annealed composition can also, importantly, display approximately the same optical characteristics as the deposited composition.
  • the deposited composition can be thermally treated such that the composition partially or wholly anneals.
  • the formed alloy can have discrete regions with elemental compositions that approximate the nanoparticle and the solid state matrix as made through the above referenced thermal decomposition or the alloy can be annealed to a single phase.
  • thermoelectric piezoelectric
  • ferroelectric phase change and electroluminescent characteristics
  • solid state materials can be used in devices like photovoltaic cells, piezoelectric crystals, thermoelectric layers, optoelectronic layers, light emitting diodes, ferroelectric layers, thin film transistors, floating gate memory devices, phase change layers, detectors of light, X-ray and gamma radiation, imaging devices, and sensor devices.
  • compositions and methods described herein generally relate to new colloidal particles (inorganic capped nanomaterials) and materials, composites, made from these nanometer scale particles.
  • the colloidal particles can be facilely produced from single or multi-component mixtures of nanoparticles and the materials can be produced thereform. These new colloidal particles, materials and the methods, described herein, may reduce the time, expense, and uncertainty in the manufacture of advanced materials.
  • Colloidal particles from which the herein described materials can be produced, are discrete particles and are generally suspendable in at least one solvent.
  • the colloidal particles are isolable, that is the colloidal particles can be isolated from reagents used in the manufacture of the colloidal particles.
  • One characteristic of many isolable colloidal particles is that the colloidal particles can be deposited from a solution and then resuspended or redissolved in the same or a different solvent.
  • colloidal particles have sizes ranging from the nanometer scale to the micron scale and can exist as mixtures with broad size ranges.
  • Nanoparticles are those particles where at least the cross-sections of the particle in two dimensions are between about 1 and about 1000 nanometers (nm).
  • Nanoparticles can be produced in a large variety of morphologies and sizes all of which are applicable herein.
  • Nonlimiting examples of the morphologies of nanoparticles include, nanocrystals, nanorods, nanoplates, nanowires, dumbbell-like nanoparticles, and dendritic nanomaterials. See Fig. 1 .
  • nanocrystals can be produced in spheres, cubes, tetrahedra, octahedra, icosahedra, prisms, cylinders, wires, branched and hyperbranched morphologies.
  • the morphology and the size of the nanoparticles do not inhibit the general method for making colloidal materials described herein; specifically the selection of morphology and size of the nanoparticle allows for the tuning and control of the properties of the colloidal material, as will become clear.
  • Non-limiting examples of nanoparticles applicable herein include: AlN, AlP, AlAs, Ag, Au, Bi, Bi 2 S 3 , Bi 2 Se 3 , Bi 2 Te 3 , CdS, CdSe, CdTe, Co, CoPt, CoPt 3 , Cu, Cu 2 S, Cu 2 Se, CuInSe 2 , CuIn (1-x) Ga x (S,Se) 2 , Cu 2 ZnSn(S 1 Se) 4 , Fe, FeO, Fe 2 O 3 , Fe 3 O 4 , FePt, GaN, GaP, GaAs, GaSb, GaSe, Ge, HgS, HgSe, HgTe, InN, InP, InSb, InAs, Ni, PbS, PbSe, PbTe, Pd, Pt, Ru, Rh, Si, Sn, ZnS, ZnSe, ZnTe, and mixtures thereof.
  • nanoparticles examples include core/shell nanoparticles like Au/PbS, Au/PbSe, Au/PbTe, Ag/PbS, Ag/PbSe, Ag/PbTe, Pt/PbS, Pt/PbSe, Pt/PbTe, Au/CdS, Au/CdSe, Au/CdTe, Ag/CdS, Ag/CdSe, Ag/CdTe, Pt/CdS, Pt/CdSe, Pt/CdTe, Au/FeO, Au/Fe 2 O 3 , Au/Fe 3 O 4 , Pt/FeO, PtVFe 2 O 3 , PtVFe 3 O 4 , FePt/PbS, FePtVPbSe, FePtVPbTe, FePtVCdS, FePt/CdSe, FePtVCdTe, CdSe/CdS, CdSe/Zn
  • an organic capping agent is trioctylphosphine oxide (TOPO), used in the manufacture of CdSe.
  • TOPO trioctylphosphine oxide
  • the TOPO capping agent prevents the agglomeration of the nanoparticle during and after the synthesis of the particle, additionally the long organic chains radiating from the capping agent on the surface of the nanoparticle assist in the suspension and/or solubility of the nanoparticle in a solvent.
  • a second type of organic capping agent is a organic thiol, often used in the manufacture of silver or gold nanoparticles.
  • organic thiols range from simple long chain alkane thiols, like dodecane thiol, to complex monothiols.
  • the long organic chain of the organic thiol capping agent assists in the suspension and/or solubility of the capped nanoparticle.
  • Other known capping agents include long-chain aliphatic amines, long-chain aliphatic phosphines, long-chain aliphatic carboxylic acids, long-chain aliphatic phosphonic acids and mixtures thereof.
  • inorganic capping agents are those soluble reagents free of organic functionality that displace organic capping agents from nanoparticles and, preferably, wherein the inorganic capped nanoparticle is dispersible, that is suspendable and/or soluble.
  • Inorganic capping agents comprises metals selected from transition metals, lanthanides, actinides, main group metals, metalloids, and mixtures thereof.
  • Inorganic capping agents further comprise soluble metal chalcogenides and/or metal carbonyl chalcogenides.
  • One aspect of the technique of replacing the organic capping agents with inorganic capping agents is the complete, or substantially complete, displacement of the organic capping agents from the nanoparticle and replacement with the inorganic capping agent. See Fig. 2 .
  • Inorganic capping agents can be neutral or ionic, can be discrete species, linear or branched chains, or two-dimensional sheets. Ionic inorganic capping agents are commonly referred to as salts, a pairing of a cation and an anion, and the portion of the salt specifically referred to as an inorganic capping agent is the ion that displaces the organic capping agent and caps the nanoparticle. Often an inorganic ion is paired with an ion that has organic functionality; the paired ion that does not displace organic capping agents is referred to herein as a counter ion. The counter ion can affect the solubility and reactivity of the inorganic capping agent as well as the inorganic capped nanomaterial but the great variability of counter ions allows for their facile replacement and a balance of desired properties.
  • the inorganic capping agents described herein are often designated by formulations derived from a variety of analytical techniques, including elemental analysis, mass spectroscopy, and NMR. These designations may or may not accurately describe the molecular compositions of these inorganic capping agents in a solution and further do not prescribe to them a specific structure. It is believed that at least some of the herein described inorganic capping agents exhibit variable solution structure equilibria, possibly dependent on temperature, concentration, purity, and other factors.
  • the inorganic capping agents are Zintl ions.
  • Zintl ions refers to homopolyatomic anions and heteropolyatomic anions that have intermetallic bonds between the same or different metals of the main group, transition metals, lanthanides, and/or actinides.
  • Non-limiting examples of Zintl ions include: As 3 3- , As 4 2- , As 5 3- , As 7 3- , As 11 3- , AsS 3 3- , As 2 Se 6 3- , As 2 Te 6 3- , As 10 Te 3 2- , Au 2 Te 4 2- , Au 3 Te 4 3- , Bi 3 3- , Bi 4 2- , Bi 5 3- , Bi 7 3- , GaTe 2- , Ge 9 2- , Ge 9 4- , Ge 2 S 6 4- , HgSe 2 2- , Hg 3 Se 4 2- , In 2 Se4 2- , In 2 Te 4 2- , Ni 5 Sb 17 4- , Pb 5 2- , Pb 7 4- , Pb 9 4- , Pb 2 Sb 2 2- , Sb 3 3- , Sb 4 2- , Sb 7 3- , SbSe 4 3- , SbSe 4 5- , SbTe 4 5- , Sb 2 Se 3- , Sb 2 Te 5 4- , Sb 2 TeA 1 Sb 4 Te 4
  • inorganic capping agents include, for example, molecular compounds derived from CuInSe 2 , CuInxGa 1-x Se 2 , Ga 2 Se 3 , In 2 Se 3 , In 2 Te 3 , Sb 2 S 3 , Sb 2 Se 3 , Sb 2 Te 3 , and ZnTe, the inorganic complexes disclosed in Roof, L. C, Kolis, J. W. Chem. Rev. 1993, 93, 1037-80 , and the inorganic complexes disclosed in Corbett, J. D. Chem. Rev. 1985, 85, 383-97 .
  • the exact stoichiometry in a solution has not yet been adequately established, this does not preclude the use herein.
  • Non-stoichiometric Zintl ions and inorganic capping agents derived from molecular compounds include, for example, inorganic capping agents derived from molecular compounds wherein excess chalcogenide is added.
  • inorganic capping agents derived from molecular compounds wherein excess chalcogenide is added include, for example, an inorganic capping agent derived from Sb 2 Te 3 with excess tellurium, [Sb 2 Te 3 Te].
  • Sb 2 Te 3 Te is an inorganic capping agent derived from Sb 2 Te 3 with excess tellurium, [Sb 2 Te 3 Te].
  • Analysis of Sb 2 Te 3 Te indicates a solution composition that contains SbTe 3 3- , Sb 2 Te 5 4- , and Sb 2 Te 7 4- by ESI-MS and a stoichiometry of Sb 2 Te 7 4- by elemental analysis.
  • these inorganic capping agents include mixtures of Zintl ions and molecular compounds.
  • These inorganic capping agents further include transition metal chalcogenides.
  • transition metal chalcogenides include the tetrasulfides and tetraselenides of vanadium, niobium, tantalum, molybdenum, tungsten, and rhenium, and the tetratellurides of niobium, tantalum, and tungsten.
  • transition metal chalcogenides further include the monometallic and polymetallic polysulfides, polyselenides, and mixtures thereof, e.g., MoS(Se 4 ) 2 2- , Mo 2 S 6 2- .
  • Core/shell nanoparticles are those particles where one nanocrystal has an outer crystalline layer with a different chemical formula.
  • Core/shell nanoparticle compositions are commonly designated through the simple notation of (core composition)/(shell composition), for example CdSe/CdS has a CdSe core and a CdS shell.
  • the crystalline layer, the shell, generally forms over the entire nanocrystal but as used herein core/shell nanoparticles refers to those nanoparticles where at least one surface of the nanocrystal is coated with a crystalline layer.
  • the inorganic capping agents may form ordered arrays on the surface of a nanocrystal these arrays differ from a core/shell crystalline layer, in part because the thickness of the array is dependent on the size of the inorganic capping agent not the concentration of reagent provided or the growth time of the layer.
  • the disclosed colloidal particles are soluble and/or suspendable in a solvent.
  • the purification of chemicals requires some isolation procedure and for inorganic materials this procedure is often the precipitation of the inorganic product.
  • the precipitation of inorganic products permits one of ordinary skill to wash the inorganic product of impurities and/or unreacted materials. The isolation of the precipitated inorganic products then allows for the selective application of those materials.
  • colloidal particles are isolable and dispersible, soluble or suspendable, in a variety of solvents. Manufacturing techniques, environmental and/or workplace rules often require the application of certain solvents. Colloidal materials dispersible in a variety of solvents are applicable for a broader use than those colloidal materials that require specific, toxic, environmentally hazardous, or costly solvents.
  • Solvents applicable herein include but are not limited to: 1,3-butanediol, acetonitrile, ammonia, benzonitrile, butanol, dimethylacetamide, dimethylamine, dimethylethylenediamine, dimethylformamide, dimethylsulfoxide, dioxane, ethanol, ethanolamine, ethylenediamine, ethyleneglycol, formamide, glycerol, methanol, methoxyethanol, methylamine, methylformamide, methylpyrrolidinone, pyridine, tetramethylethylenediamine, triethylamine, trimethylamine, trimethylethylenediamine, water, and mixtures thereof.
  • the above-described colloidal particles can be made by mixing the nanoparticle in form of powder, suspension or a colloidal solution with the inorganic capping agent in accordance with the techniques described herein.
  • the mixing of the nanoparticle with the inorganic capping agent causes a reaction of the nanoparticle with the inorganic capping agent and rapidly produces insoluble and intractable materials.
  • a mixture of immiscible solvents is used to control the reaction of the nanoparticle with the inorganic capping agent. Immiscible solvents facilitate a rapid and complete exchange of the organic capping agents with the inorganic capping agents.
  • the inorganic capping agent is dissolved in a polar solvent, a first solvent, while the nanoparticle is dissolved in an immiscible, generally non-polar, solvent, a second solvent. These two solutions are then combined in a single vessel.
  • Non-limiting examples of polar solvents include 1,3-butanediol, acetonitrile, ammonia, benzonitrile, butanol, dimethylacetamide, dimethylamine, dimethylethylenediamine, dimethylformamide, dimethylsulfoxide, dioxane, ethanol, ethanolamine, ethylenediamine, ethyleneglycol, formamide, glycerol, methanol, methoxyethanol, methylamine, methylformamide, methylpyrrolidinone, pyridine, tetramethylethylenediamine, triethylamine, trimethylamine, trimethylethylenediamine, water, and mixtures thereof.
  • Non-limiting examples of non-polar solvents include pentane, pentanes, cyclopentane, hexane, hexanes, cyclohexane, heptane, octane, isooctane, nonane, decane, dodecane, hexadecane, benzene, 2,2,4-trimethylpentane, toluene, petroleum ether, ethyl acetate, diisopropyl ether, diethyl ether, carbon tetrachloride, carbon disulfide, and mixtures thereof; provided that the non-polar solvent is immiscible with the polar solvent.
  • Other immiscible solvent systems that are applicable include aqueous-fluorous, organic-fluorous, and those using ionic liquids.
  • the nanoparticle reacts with the inorganic capping agent at or near the solvent boundary, the region where the two solvents meet, and a portion of the organic capping agent is exchanged/replaced with the inorganic capping agent. That is, the inorganic capping agent displaces an organic capping agent from a surface of the nanoparticle and the inorganic capping agent binds to the surface of the nanoparticle. Without wishing to be bound by theory, it is thought that this process continues until an equilibrium is established between the inorganic capping agent on a nanoparticle and the free inorganic capping agent.
  • the equilibrium favors the inorganic capping agent on a nanoparticle, although other equilibria are applicable for making mixed colloidal particles.
  • the herein described immiscible solvent method of forming nanoparticles capped with inorganic capping agents has the added benefit of providing for the extraction of the organic capping agents from the inorganic capped nanocrystals.
  • the extraction of the organic capping agent can provide a solution of an inorganic capped nanocrystal that is substantially free of the organic capping agent.
  • substantially free means the relative concentration of the organic capping agent to the nanoparticle in the solution of the inorganic capped nanocrystal is less than 10%, 5%, 4%, 3%, 2%, 1%, 0.5%, and/or 0.1% of the concentration in a solution of the organic capped nanocrystal.
  • One means for determining if a solution is substantially free of the organic capping agent is IR spectroscopy and the observation of the absence of C-H stretching frequencies.
  • the uncharged organic capping agent is preferably soluble in the non-polar solvent and is thereby physically separated from the nanocrystals, affording the opportunity to remove all of the organic capping agent from the inorganic capped nanocrystal.
  • This facile method of making inorganic capped nanoparticles allows for the selective precipitation of these colloidal particles, the selective precipitation of excess inorganic capping agent, or the direct use of the colloidal particle solution in the manufacture of films, crystals, or devices.
  • colloidal particles examples include Au•AsS 3 , Au•Sn 2 S 6 , Au•SnS 4 , Au•Sn 2 Se 6 , Au•In 2 Se 4 , Bi 2 S 3 •Sb 2 Te 5 , Bi 2 S 3 •Sb 2 Te 7 , Bi 2 Se 3 •Sb 2 Te 5 , Bi 2 Se 3 •Sb 2 Te 7 , CdSe•Sn 2 S 6 , CdSe•Sn 2 Te 6 , CdSe•In 2 Se 4 , CdSe•Ge 2 S 6 , CdSe•Ge 2 Se 3 , CdSe•HgSe 2 , CdSe•ZnTe, CdSe•Sb 2 S 3 , CdSe•SbSe 4 , CdSe•Sb 2 Te 7 , CdSe•In 2 Te 3 , CdTe•Sn 2 S 6 , CdTe•Sn 2 Te 6 , CdTe•In 2
  • the denotation Au•Sn 2 S 6 refers to a Au nanocrystal capped with a Sn 2 S 6 inorganic capping agent. Charges on the inorganic capping agent are omitted for clarity.
  • This nomenclature [nanocrystal]•[inorganic capping agent] is used throughout this description. The specific percentages of nanoparticle and inorganic capping agent vary between the colloidal particles.
  • the energy dispersive X-ray (EDX) spectrum of a sample of CdSe•Sn 2 Se 6 shows a composition that corresponds to approximately 95 % CdSe nanocrystals and about 5 % Sn 2 Se 6 .
  • the EDX spectrum of Au•Sn 2 Se 6 shows a composition that corresponds to approximately 90 % Au nanocrystals and 10 % Sn 2 Se 6 . See Fig. 5 . Without being bound to theory, the different percentages of Sn 2 Se 6 observed in the samples in Fig. 5 are believed to correlate with the thio-affinity of the nanocrystal surface and surface area.
  • the described method does not affect the extent of aggregation of the colloidal particles.
  • dynamic light scattering shows that a sample of 5 nm Au nanoparticles coated with the inorganic capping agent Sn 2 S 6 (Au•Sn 2 S 6 ) can have an average hydrodynamic colloidal particle size of about 8 nm and show no aggregation. See Fig. 6 .
  • a sample of 6 nm CdSe nanoparticles coated with the inorganic capping agent Sn 2 S 6 (CdSe•Sn 2 S 6 ) has an average colloidal particle size of about 8 nm and shows no aggregation. See Fig. 6 .
  • Fig. 9 shows a white light photograph of colloidal particles prepared from 3.6 nm CdSe nanocrystals. The color of the samples (indicative of the electronic characteristics of the nanocrystal) did not significantly change when the CdSe is capped with different inorganic capping agents.
  • a single inorganic capping agent here Sn 2 S 6 4- , can cap a wide variety of nanoparticles, see e.g., Fig. 9 .
  • Figure 10 shows that the herein described colloidal particles are stable and soluble in a variety of solvents and that the electronic characteristics of the underlying nanoparticle are neither changed by the presence of the inorganic capping agent nor the solvent. Had the electronic characteristics of the nanoparticle been affected by the solvent then the optical absorption of the nanoparticle would have changed. See also Fig. 12 .
  • Fig. 11 shows photoluminescence under UV excitation and lists quantum yields from a sample of CdSe•Sn 2 S 6 in different solvents. See Fig. 12 for a white light photograph of the same samples.
  • Fig. 12 includes a series of plots of the photoluminescence of a sample of CdSe•Sn 2 S 6 in different solvents showing that the emission maximum does not significantly change between solvents.
  • the above described method can be adapted to make a wide variety of colloidal particles.
  • Adaptations of the method include adding two different inorganic capping agents to a single nanoparticle (e.g., Au•(Sn 2 S 6 ;In 2 Se 4 ); Cu 2 Se•(In 2 Se 4 ;Ga 2 Se 3 )), adding two different nanoparticles to a single inorganic capping agent (e.g., (Au;CdSe)•Sn 2 S 6 ; (Cu 2 Se;ZnS)•Sn 2 S 6 ), adding two different nanoparticles to two different inorganic capping agents (e.g., (Au;CdSe)•(Sn 2 S 6 ;In 2 Se 4 )), and/or additional multiplicities.
  • a single nanoparticle e.g., Au•(Sn 2 S 6 ;In 2 Se 4 ); Cu 2 Se•(In 2 Se 4 ;Ga 2 Se 3
  • inorganic capping agents to a nanoparticle
  • concentration, nucleophilicity, capping agent to nanoparticle bond strength, and crystal face dependent capping agent to nanoparticle bond strength the inorganic capping of the nanoparticle can be manipulated to yield other combinations.
  • a nanoparticle has two faces, face A and face B, and that the bond strength of the organic capping agent to face A is twice that of the bond strength to face B.
  • the organic capping agents on face B would be preferentially exchanged when employing the herein described methodology.
  • Isolation and reaction of this intermediate species, having organic and inorganic capping agents, with a second inorganic capping agent would produce a colloidal particle with a first inorganic capping agent on face B and a second inorganic capping agent on face A.
  • the preferential binding of inorganic capping agents to specific nanoparticle faces can yield the same result from a single mixture of multiple inorganic capping agents.
  • Another aspect of the disclosed method is the possibility of a chemical reactivity between inorganic capping agents.
  • a first inorganic capping agent bound to the surface of a nanocrystal and reactive with a second inorganic capping agent can directionally react with the second inorganic capping agent.
  • This methodology provides for the synthesis of colloidal particles that could not be selectively made from a solution of nanoparticle and inorganic capping agents.
  • the interaction of the first inorganic capping agent with the nanoparticle controls both the direction and scope of the reactivity of the first inorganic capping agent with the second inorganic capping agent.
  • this methodology controls what part of the new inorganic capping agent binds to the nanocrystal.
  • the result of the addition of a combined-inorganic capping agent capping to a nanocrystal by other methods would produce a random arrangement of the combined-inorganic capping agent on the nanocrystal.
  • colloidal particles involve the mixing of a nanoparticle in a non-polar organic solvent with a purified colloidal particle in a polar organic solvent.
  • the colloidal particle in the polar solvent is the inorganic capping agent.
  • Still another aspect of the current disclosure is the bridging of colloidal particles with metal ion complexing agents. See Fig. 24 .
  • bridging means that one or more metal ions individually bind, ionically or covalently, binding sites on the exterior of a plurality of colloidal particles.
  • binding sites are parts of the inorganic capping agent that is disposed perpendicular to a surface on the nanoparticle.
  • inorganic capping agents include anionic and neutral capping agents.
  • anionic inorganic capping agents When, for example, anionic inorganic capping agents are bound to the surface of a nanoparticle, the anionic charge associated with the inorganic capping agent remains (providing a theoretical basis for electrostatic repulsion between colloidal particles having anionic inorganic capping agents).
  • a cationic ion preferably a cationic metal ion, still more preferably a polycationic (wherein the charge on the metal ion is greater than 1) metal ion to the colloidal particle can produce a colloidal particle with the cationic ion bound to a surface of the colloidal particle, specifically to the inorganic capping agent.
  • the cationic ion can bind to the surface of a second colloidal particle thereby bridging between the two colloidal particles.
  • the cationic ion is a transition metal ion, a main group ion, a lanthanide ion, or an actinide ion. More preferably, the cationic ion is selected from those ions that can impart advanced electronic, magnetic (e.g., Mn 2+ , Co 2+ ), or photophysical properties on the bridged colloidal particles.
  • the cation ion is Pt 2+ , Zn 2+ , Cd 2+ , Mn 2+ , Mn 3+ , Eu 2+ , Fe 2+ , Fe 3+ , Co 2+ , Ge 4+ , Cu 2+ , Cu + , Pb 2+ , Bi 3+ , Sb 3+ , In 3+ , Ga 3+ , Au + , Au 3+ , Ag + , Sn 2+ , Sn 4+ , or Hg 2+ .
  • a descriptive drawing of the bridging of a colloidal particle with a cation ion is shown in Fig. 24 .
  • a polycondensation reaction When the addition of the cationic ion to the colloidal particle is conducted on a scale wherein there is a multiplicity of colloidal particles, the binding and bridging of the colloidal particles is termed a polycondensation reaction.
  • a controlled polycondensation reaction yields colloidal materials.
  • the selection of cationic ion and polycondensation reaction conditions allows for control of the three-dimensional structure of the colloidal material. Without being bound by theory, these polycondensation reactions are envisioned as behaving analogously to molecular self-assembled three-dimensional arrays.
  • colloidal materials are samples of the herein described colloidal particle in a solid form.
  • the form can be ordered or disordered.
  • the nanoparticle may have a crystalline, that is, ordered internal structure but the precipitation of the colloidal particles may produce a random (disordered) arrangement of particles.
  • the controlled dissolution or spontaneous self-assembly of the colloidal particles can yield ordered arrays of particles.
  • the careful deposition of thin layers of colloidal arrays can yield ordered arrays dependent on the packing of the colloidal particle in three dimensional space.
  • the deposition of colloidal particles of nanocrystals that are roughly spherical has yielded hexagonal close-packed arrays of colloidal particles or cubic close-packed arrays of colloidal particles. See Figs. 3, 4 , 25 , and 26 .
  • Such selective deposition of colloidal particles has advanced materials applications for which the selection of the nanoparticle and the ordering of the three dimensional array can change, for example, the physical, magnetic, optical and/or electronic characteristics of the material.
  • Nanocrystals of different size and functionality can be induced to self-assemble into ordered binary superlattices retaining the size tunable properties of their constituents.
  • a variety of binary superlattices can be built from monodisperse PbS, PbSe, CoPt 3 , Fe 2 O 3 , Au, Ag, Pd and nanocrystals, mixing and matching these nanoscale building blocks to yield multifunctional nanocomposites. See, for example, Figure 26 .
  • Binary superlattices can be isostructural with NaCl, CuAu, CsCl, AlB 2 , MgZn 2 , MgNi 2 , Cu 3 Au, Fe 4 C, CaCu 5 , CaB 6 , NaZn 13 and cub- AB 13 and other compounds emphasizing the parallels between nanoparticle assembly and atomic scale crystal growth.
  • the deposition of layers of the colloidal particles to make colloidal material thin films is another aspect of the current disclosure. See Fig. 35 .
  • multiple film deposition methodologies are available.
  • One method that is applicable to form colloidal material thin films is a reverse Langmuir-Blodgett technique.
  • the insolubility of the colloidal particle in nonpolar solvents permits the monolayer deposition of films of the colloidal particle on a substrate.
  • Multiple application of the Langmuir-Blodgett technique can be employed to grow multilayer films of the colloidal particle or mixed layer films of colloidal particles.
  • a second applicable technique for the deposition of layers of the colloidal particles to make colloidal material thin films is spin coating.
  • a solution of the colloidal particle is applied to a substrate and the substrate and solution are rapidly rotated to leave a thin layer of the solution on the substrate, this solution is then dried leaving the colloidal material thin film.
  • the use of multiple solvents described above provide control in the manufacture of these films.
  • the wetting of the substrate by the colloidal particle solution is an important factor in achieving uniform thin films and the ability to apply the colloidal particle in a variety of different solvents enhances the commercial applicability of this technique.
  • One method to achieve uniform wetting of the substrate surface is to match the surface free energy of the substrate with the surface tension of the liquid (colloidal particle solution). Theoretically, the perfect wetting of a substrate by a colloidal particle solution would yield a uniform colloidal material thin film on the substrate.
  • Additional techniques for the deposition of layers of the colloidal particles to make colloidal material thin films include doctor blading, spin coating, spray coating, spray pyrolysis, dipping/dip-coating, sputtering, printing, inkjet printing, stamping and combinations of spray coating, spray pyrolysis dipping, sputtering, printing and with spin coating.
  • colloidal material can be produced through the bridging of the colloidal particles with complexing agents thereby forming complexed colloidal particles and/or complexed colloidal materials; a distinction that is dependent, in part, on the amount of complexing agent employed.
  • complexed colloidal particles can be formed by the addition of a complexing agent to a colloidal particle.
  • complexed colloidal particles include but are not limited to combinations of a cationic ion-complexing agent and an anionic colloidal particle.
  • the herein described colloidal particle can complex with, for example, transition metal cations, transition metal cation complexes, main group cations.
  • complexing agents include chromium, manganese, iron, cobalt, nickel, copper, zinc, ruthenium, rhodium, palladium, silver, cadmium, osmium, iridium, platinum, gold, and mercury cations, e.g., Pt 2+ , Zn 2+ , Cd 2+ , Mn 2+ , Mn 3+ , Eu 2+ , Fe 2+ , Fe 3+ , Co 2+ , Ge 4+ , Cu 2+ , Cu + , Pb 2+ , Bi 3+ , Sb 3+ , In 3+ , Ga 3+ , Au + , Au 3+ , Ag + , Sn 2+ , Sn 4+ , and Hg 2+ .
  • the resultant material, complexed colloidal material can be insoluble and described as a polymeric material. See Fig. 24 .
  • the complexed colloidal material is formed by the alternating addition of a substrate to a solution of colloidal particles and to a solution of complexing agent.
  • the substrate preferably, has a sufficient affinity for the first material, whether colloidal particles or complexing agents, such that a layer of the first material uniformly deposits on the surface of the substrate.
  • substrates wherein the colloidal particle could be the first material include but are not limited to mono or multilayers of copper, silver, gold, nickel, palladium, platinum, alloys, and amalgams thereof.
  • thiophilic substrates can be employed.
  • thiophilic means having a thermodynamic preference for binding to sulfur, selenium, and/or tellurium.
  • thiophilic substrates include monolayers, multilayers, or bulk amounts of silver, gold, and other known thiophilic substrates.
  • Another substrate applicable when the first material is a neutral or anionic colloidal particle is a positively charged substrate.
  • Substrates made from glass, sapphire, quartz, silicon, or other solid materials can be manipulated to have a positive charge through many known methods. For example, the chemical treatment of a substrate with an amine functionalized siloxane can produce a positively charged surface on the substrate.
  • Still another embodiment of complexed colloidal materials includes the combination of cationic polymers with the colloidal particle.
  • an alternating dip coating process can be employed to build layers of a cationic polymer and a colloidal particle. See Fig. 35 .
  • the first material added to a substrate can be either a cationic polymer or a colloidal particle.
  • Known methods to form films of polymers on substrates are applicable herein and often a substrate is first coated with the polymer.
  • Examples of polymers include the polyquaternium polymers, e.g., poly(diallyldimethylammonium) chloride (polyquaternium-6 (CAS#: 26062-79-3); PDDA) and polyethyleneimine (PEI).
  • the alternating dip coating can include repetitively, dipping a substrate in a first solution, rinsing the substrate, dipping the substrate in a second solution, and rinsing the substrate.
  • Non-limiting examples of Layer-by-Layer assemblies made by this method include 10, 20, and 30 layer films of CdSe/ZnS•SnS 4 and PDDA, and 10, 20, and 30 layer films of Au•SnS 4 and PDDA.
  • a substrate prior to any dipping can preferentially bind the colloidal particle thereby the first solution is a solution having the colloidal particle dispersed therein. Additional combination procedures are available, for example first spin coating a substrate with a solution of a colloidal particle then dipping the substrate in a solution of a cationic ion and then repeating.
  • Complexed colloidal materials can further yield ordered arrays. See Figs. 25-26 .
  • the complexing agent can be a non-polymeric material.
  • One applicable type is cationic amines (NR 1 R 2 R 3 R 4+ ) and phosphines (PR 1 R 2 R 3 R 4+ ) with aliphatic substituents, for example, where at least one R group has a C 6 , C 7 , C 8 , C 9 , C 10 , C 11 , C 12 , C 13 , C 14 , C 15 , C 16 , C 18 , C 20 , C 22 , C 24 , C 26 , C 28 , C 30 , or C 40 alkyl chain.
  • One operative example is the dimethylbisdodecylammonium cation (N(CH 3 ) 2 (C 12 H 25 ) 2 + ).
  • the addition of the cationic amine or phosphine can be by a biphasic transfer of the colloidal particle form a polar solvent into a non-polar solvent.
  • One operative example includes the dissolution of a dodecylammonium Sn 2 S 6 salt in a non-polar solvent and the dissolution of CdSe•Sn 2 S 6 in a polar solvent.
  • the cation exchange can transfer the colloidal particle into the non-polar solvent.
  • ink-jet deposition Another technique wherein the ability to select the solvent in which the colloidal material is dissolved and from which it is deposited is ink-jet deposition. Ink-jet deposition often requires the ability to adjust liquid surface tensions to applicable ranges.
  • One easy method for adjusting the surface tension of a liquid containing colloidal particles is the blending or mixing of a multiplicity of solvents.
  • colloidal particles to make non-thin film solids.
  • the described colloidal particles are deposited by bulk techniques to yield three dimensional solids.
  • Known bulk deposition techniques include pressing of powders, growth of three-dimensional ordered arrays, painting, printing, e.g., the hot pressing of colloidal materials to yield colloidal matrices and/or alloys.
  • Still another aspect of the techniques described above for the production or deposition of colloidal materials is the production or deposition of mixed, colloidal particle, solids.
  • These hetero-colloidal materials comprise a plurality of colloidal particles in the resulting solid material.
  • multiple techniques can be used to produce hetero-colloidal materials. Non-limiting examples include, mixing of colloidal particles in a solvent followed by deposition of a hetero-colloidal material alternating deposition of colloidal material films to produce a layered hetero-colloidal material, multispray coating of a substrate, and blending of colloidal material solids followed by pressing into a cohesive material.
  • hetero-colloidal materials described herein is a binary superlattice.
  • Binary superlattices are those organized structures wherein the three-dimensional packing of two different nanoparticles produces an ordered structure. Multiple physical and chemical characteristics can facilitate the production of binary superlattices, for example, nanoparticle size, nanoparticle shape, and nanoparticle Coulombic potential.
  • This assembly of two different colloidal particles into a binary superlattice is a general and inexpensive method to produce multiple hetero-colloidal materials with precise control of the chemical composition and physical properties. See Fig. 26 .
  • thermal treatment of the herein described colloidal materials is the thermal treatment of the herein described colloidal materials.
  • many of the inorganic capping agents are precursors to inorganic materials (matrices) and low-temperature thermal treatment of these inorganic capping agents provides a gentle method to produce crystalline films from these materials.
  • the thermal treatment of colloidal materials yields, for example, ordered arrays of nanoparticles within an inorganic matrix, hetero-alloys, or alloys.
  • the thermal treatment of the colloidal material includes heating to a temperature less than about 350, 300, 250, 200, and/or 180 °C.
  • Still another aspect of the current disclosure is a low mass/volume loss on thermal treatment.
  • the herein described colloidal materials lose less than about 20%, 15%, 10%, and/or 5% of their mass, as determined by thermogravimetric analysis (TGA), upon a thermal treatment up to about 400 and/or 450 °C.
  • TGA thermogravimetric analysis
  • CdSe/ZnS•Sn 2 S 6 loses about 5% of its mass upon heating to about 450 °C
  • the (NH 4 ) 4 Sn 2 S 6 used as the inorganic capping agent for the colloidal particle loses about 30 % of its mass over the same temperature range. See Figure 37 .
  • colloidal matrices are arrays of nanoparticles within an inorganic matrix.
  • the inorganic matrix separates the nanoparticles.
  • the inorganic matrix can be a glass, a solid, or a crystalline material.
  • the order of the array of nanoparticles can be short range or long range.
  • Very dilute samples of nanoparticles in the inorganic matrix are expected to have lower relative ordering than concentrated samples wherein the nanoparticles may be ordered prior to and preferably after the formation of the inorganic matrix.
  • Colloidal matrices can be homo-colloidal matrices or hetero-colloidal matrices and can be produced as thin films, films, coatings, and/or solids.
  • a homo-colloidal matrix is a colloidal matrix having one species of nanoparticle and an inorganic matrix derived from a single inorganic capping agent.
  • Non-limiting examples of homo-colloidal matrices include SnS 2 (Au), SnS 2 (CdSe), SnS 2 (CdSe/CdS), and SnS 2 (PbS). See Figs. 13-15 .
  • SnS 2 (Au) refers to Au nanocrystals in a matrix having the approximate formula SnS 2 .
  • a hetero-colloidal matrix is a colloidal matrix having, for example, a multiplicity of nanoparticle species in an inorganic matrix derived from a single inorganic capping agent, or one species of nanoparticle in an inorganic matrix derived from a multiplicity of inorganic capping agents.
  • One example of the latter hetero-colloidal matrix is the matrix produced by thermally treating a mixture of CdSe•Sn 2 S 6 and CdSe/CdS•Sn 2 S 6 , denoted SnS 2 (CdSe;CdSe/CdS).
  • hetero-colloidal matrices include those formed by selective deposition of colloidal materials in confined spatial arrangements followed by thermal treatment to form the inorganic matrix.
  • the layered, structured, or patterned deposition of a plurality of colloidal materials followed by thermal treatment to form an inorganic matrix can create solid-state architectures that are not available by other known methodologies.
  • One illustrative example of the present embodiment is the patterned deposition of CdSe•Sn 2 S 6 nanoparticles followed by the patterned deposition of Au•Sn 2 S 6 .
  • the thermal treatment of this illustrative example can produce three distinct material regions within a single inorganic matrix derived from Sn 2 S 6 4- , that is, this patterned colloidal matrix will include regions of matrix encapsulated CdSe nanoparticles, regions containing a matrix encapsulated mixture of CdSe and Au nanoparticles, and regions of matrix encapsulated Au nanoparticles.
  • the colloidal matrices can be produced in thin films, films, coatings, solids and/or mixed solids. Moreover, the colloidal matrices can be produced in bulk, layered, structured, or patterned arrangements on a substrate. Additionally, the procedure described herein can yield colloidal matrices that effectively preserve the electronic characteristics of the nanoparticle after thermal treatment.
  • Fig. 15 shows the optical absorbance spectrum of thin films of an organic capped CdSe (CdSe•(organic capping agent(s))), an inorganic capped CdSe (CdSe•Sn2S6), and a CdSe colloidal matrix (SnS 2 (CdSe)). The absorption at approximately 600 nm is apparent in all samples and is characteristic of the presence of the CdSe nanocrystal.
  • alloys made from a nanoparticle and an inorganic capping agent. Alloys are continuous homogeneous phases of a composition and herein alloys are produced by the thermal treatment of the disclosed colloidal particles. Similar to the colloidal matrices, the formulation of the alloy is dependent on the nanoparticle and inorganic capping agent. Unlike the colloidal matrices, the formation of the alloy involves the destructive reaction of the inorganic capping agent, and/or optionally additional reagent(s), with the nanoparticle, herein a destructive reaction means the nanoparticle loses at least one aspect of its defining physical characteristic, examples include size, shape, photoactivity, formulation.
  • Non- limiting examples include the formation of a Cd x Sn y Se z alloy from CdSe•Sn 2 S 6 colloidal particles; the formation of a CuInSe 2 alloy from any one of the following colloidal particles: Cu 2 Se•In 2 Se 3 , Cu 2 Se•In 2 Se 4 , Cu 2 S•In 2 Se 3 , and/or Cu 2 S•In 2 Se 4 , the formation of a CuZnSnS 4 alloy from a mixture of Cu 2 S•Sn 2 S 6 and ZnS•Sn 2 S 6 ; and the formation of Cu 2 In 1 •Ga x Se 2 (e.g., Cu 2 In 0.5 Ga 0.5 Se 2 and Cu 2 In 0.9 Ga 0.1 Se 2 ) alloy from Cu 2 Se•(In 2 Se 4 :Ga 2 Se 3 ). See Fig. 40A&B .
  • hetero-alloys are solid state materials formed from the thermal treatment of a colloidal material that is characterized by a multiplicity of domains, wherein the domains may have different formulations and/or crystal structures and/or crystallinity. Whether a thermal treatment of a colloidal material forms an alloy or a hetero- alloy is often difficult to determine, but, without being bound by theory, it is believed that a lower temperature thermal treatment limits atom mobility and therefore prohibits the formation of a homogeneous phase (alloy).
  • the structure of the resulting alloy or hetero-alloy is dependent on the formulation of the colloidal particle.
  • a Bi 2-x Sb x Te 3 alloy or hetero-alloy made from a colloidal material that has a high Bi:Sb ratio has a significantly smaller crystal domain than a Bi 2-x Sb x Te 3 alloy or hetero-alloy made from a colloidal material that has a low Bi:Sb ratio.
  • Fig. 19 Not only do the two materials have different crystal domain sizes, EDS spectra indicate that the relative concentration of Bi in the latter sample is indeed lower than in the former. See Fig. 19 .
  • This comparative example indicates that multiple hetero-alloys can be produced from identical starting materials and that the relative composition of the alloy can be controlled by selective synthesis of the precursor colloidal material. See Fig. 18 .
  • the resultant material from the thermal processing of PbTe•Sb 2 Te 3 can be described as either a hetero-alloy or a colloidal matrix depending on the structure of the PbTe in the final material, still further the resultant material can be comprised of both a hetero-alloy and a colloidal matrix.
  • One reaction condition that may affect the characteristics of the resultant materials is the relative concentration of the nanoparticle.
  • the dilution in the solid phase of the nanoparticle in an excess of the inorganic capping agent can lead to smaller nanoparticles in the resultant material.
  • the concentration of the nanoparticle can be sufficiently high that the resultant materials can be a phase corresponding to the composition (or reaction product) of the nanoparticle and optionally include phase corresponding to the composition of the inorganic capping agent.
  • Ostwald ripening can affect the phases in the materials.
  • the reactive loss of a chalcogenide can further facilitate the formation of colloidal matrices, alloys, and/or hetero-alloys.
  • the reactive loss of sulfur can facilitate the formation of selenium and/or tellurium based materials.
  • This reactive loss of chalcogenide can be facilitated by the addition of an excess of a selenium or tellurium containing inorganic capping agent and/or through the addition of an excess of selenium or tellurium.
  • Non-limiting examples include the thermal processing of Cu 2 S•In 2 Se 3 and/or Cu 2 S•In 2 Se 4 where selenium reacts to displace sulfur, see Fig.
  • selenides or tellurides can be doped into the formation of colloidal matrices, alloys or heteroalloys by reactive loss of a chalcogenide.
  • selenium can be doped into a reaction that provides a telluride colloidal matrix, alloy or heteroalloy by reactive loss of sulfur by the addition of an amount of selenide-containing inorganic capping agent to the colloidal material.
  • tellurium can be doped into a selenide colloidal matrix, alloy or heteroalloy by reactive loss of sulfur by the addition of an amount of telluride-containing inorganic capping agent to the colloidal material.
  • selenium can be doped into a tellurium containing alloy by the addition of an amount of the selenium-containing inorganic capping agent Sb 2 Se 3 to the colloidal particle Bi 2 S 3 •Sb 2 Te 7 or Bi 2 S 3 •(Sb 2 Te 3 ;Sb 2 Se 3 ), the admixture can then be thermally processed to form an n-doped Bi 2-x Sb x Te 3-y Se y . See Figs. 28-29 .
  • the balancing of thermal stability against reactivity can yield materials where some nanocrystals react and others alloy.
  • mixing the processes of alloying and hetero-alloying ion capped Bi 2 S 3 •Sb 2 Te 3 and PbTe•Sb 2 Te 3 yields a (PbTe) (Bi 2-x Sb x Te 3 ) hetero-alloy.
  • the thermal processing of a colloidal material that comprises a mixture of Au•Sb 2 Te 3 and Bi 2 S 3 •Sb 2 Te 3 yields a (Au)(Bi 2-x , Sb x Te 3 ) heteroalloy where discrete Au nanocrystals can be observed in the TEM images. See Fig. 34 .
  • the colloidal materials, colloidal matrices, and alloys are fabricated by a deposition on a substrate.
  • substrates include but are not limited to silicon, amorphous hydrogenated silicon, silicon carbide, silicon dioxide, silicon nitride, aluminum oxide, aluminum nitride, carbon, hydrogenated carbon, gallium nitride, gallium arsenide, germanium, silicon-germanium, indium tin oxide, boron carbide, boron nitride, borosilicate, cerium oxide, tin oxide, zinc titanate, a glass, a metal, an organic semiconductor, a polymeric material or a combination thereof.
  • organic semiconductors and/or polymeric materials include polycarbonates, poly(3-hexylthiophene), poly(p-phenylene vinylene), poly(9,9'-dioctylfluorene-co-benzothiadiazole) ("F8BT"), poly(9,9'-dioctylfluorene-co- bis-N,N'-(4-butylphenyl)-bis-N,N'-phenyl-1 ,4-phenylenediamine), poly(9,9'-dioctylfluorene-co-bis-N,N'-(4-butylphenyl)diphenylamine) (“TFB”), poly(4,4'-oxydiphenylene-pyromellitimide) ("Kapton”), polyethylene terephthalate (e.g., "Mylar”), poly(paraphenylene terephthalamide) (e.g., "Kevlar”), poly(
  • Yet another embodiment of the materials and methods disclosed herein is the deposition of colloidal matrices, alloys, or hetero-alloys on a surface to form an advanced material, a printed circuit, a photovoltaic cell, a piezoelectric crystal, a thermoelectric layer, an optoelectronic layer, a light emitting diode, a ferroelectric layer, a thin film transistor, a floating gate memory device, a phase change layer, a sensor device, detectors of light, X-ray and gamma-radiation, an imaging device. See Fig. 22 .
  • colloidal materials disclosed herein are applicable for the printing or deposition of colloidal matrices, alloys, or hetero-alloys through the application and, optionally, heating of the colloidal material on a substrate.
  • Representative examples of the application of the disclosed colloidal materials include sputter deposition, electrostatic deposition, spray deposition, spin coating, inkjet deposition, laser printing (matrices).
  • An alternative method of deposition is the electrochemical deposition of a colloidal matrix from a solution of a colloidal material.
  • the low temperature formation of the colloidal matrix, alloy, or hetero-alloy makes the disclosed methodology compatible with photolithographic patterning, for example, wherein a photolithographic applied substrate mask is removed after the thermal treatment of the colloidal material.
  • thermoelectric energy conversion is an all-solid-state effect that converts thermal gradients directly to electrical energy without an electromechanical generator.
  • the derived voltage and power, work drains the heat from the location of the thermal gradient.
  • Materials that display thermoelectric energy conversion are useful in heat pumps, power generators, and thermoelectric coolers. Thermoelectric devices have no moving parts and therefore have advantages in reliability, silent operation, high power density, and high efficiency for moderate power applications.
  • thermoelectric materials can be used for cooling by driving current through the material.
  • thermoelectric figure of merit in the disclosed materials is tunable.
  • the thermoelectric figure of merit, zT, for the Bi 2-x Sb x Te 3 material is greater than 0.7, 1, 1.5, 2, and/or 3.
  • Aqueous NH 4 OH solution (8 mL, 28-30% of NH 3 ) was mixed with aqueous (NH 4 ) 4 Sn 2 S 6 (0.5 mL, ⁇ 0.1 M) or Na 4 SnS 4 (0.3 mL, ⁇ 0.1 M).
  • Hexane (6 mL) and toluene solution of 3-10 nm CdSe or 6.5-nm CdSe/ZnS NCs (1 mL, ⁇ 25mg/mL) were added to the same vial and the mixture was vigorously stirred until the phase transfer of NCs from the organic phase into aqueous phase was completed.
  • the aqueous phase was rinsed 3 times with hexane and filtered through a 0.45- ⁇ m PTFE filter.
  • a minimal amount of acetonitrile was added to precipitate the colloidal particles.
  • the colloidal particles were collected by centrifuging, redispersed in water and centrifuged/filtered to remove traces of insoluble materials, if any.
  • Nanoparticle Inorganic Capping Agent Comments Au nanocrystals Sn 2 S 6 4- , Sn 2 Se 6 4- , AsS 3 3- , In 2 Se 4 2- Form fcc superlattices, highly conductive.
  • Example 5 a series of Bi 2 S 3 •Sb 2 Te 7 samples can be prepared where the Bi to Sb ratio is changed.
  • the following ratios of Bi to Sb were prepared: 5% Bi/ 95% Sb; 20% Bi/ 80% Sb; 40% Bi/ 60% Sb; 60% Bi/ 40% Sb; 95% Bi/ 5% Sb.
  • the samples were dried by evaporation of hydrazine under a stream of N 2 .
  • the silver-black solids were annealed at 350 °C under N 2 and the metallic powder analyzed. See Figs. 16-20 and 27-29 .
  • a highly-doped silicon wafer with a 100 nm thick thermal silicon oxide gate dielectric was patterned with bottom Ti/Au electrodes on the silicon oxide by photolithography. This wafer was washed with acetone, isopropanol, and ethanol, then plasma cleaned in air for 30 min. Under inert atmosphere, the wafer was covered with several drops of the solution prepared in Example 5. The sample was allowed to stand for 20 min and then was spun according to the following series of steps: 1) spun at 450 rpm for 20 s; 2) spun at 900 rpm for 20 s; 3) spun up to 4000 rpm within 20 s; and then 4) spun at 4000 rpm for 20 s. The wafer, coated with a mirror-like film, was heated to 350 °C for 90 min to anneal the composite.
  • Substrates were freshly hydrophilized by 15-min treatment with oxygen plasma.
  • the colloidal particle was then deposited by drop-casting at 80 °C or by spray-coating.
  • the homogeneity and thickness of the drop-cast films were adjusted by controlling the volume and the concentration of colloidal particle in a solution. 1-10% v/v DMSO were usually added to N 2 H 4 solutions to improve homogeneity of drop-cast films.
  • For spray coating glass substrates were placed on a hot plate at 100-200 °C, while a (Bi,Sb) 2 Te 3 NC-ink solution was applied at a sprayer pressure of 15-20 psi using N 2 as a carrier gas. The film thickness was adjusted by the number of applied spraying cycles, typically 5 to 80.
  • As-deposited (Bi,Sb) 2 Te 3 films were heated at 300 °C/hour and annealed at 300 °C for 15 min, followed by slow cooling to room temperature.
  • Colloidal particles and more particularly colloidal matrices formed using techniques as described herein may be formed into various semiconductor materials and structures.
  • the quantum mechanical coupling energy can be approximated as ⁇ ⁇ h ⁇ ⁇ e x p ⁇ 2 m * ⁇ E / ⁇ 2 1 / 2 ⁇ x , where h is Planck's constant, ⁇ is the tunneling rate between two nanocrystal neighbors, m * is the carrier effective mass, ⁇ E and ⁇ x are the height of the tunneling barrier and the shortest edge-to-edge distance between the nanocrystals, respectively.
  • the original organic ligands rendered nanoparticle films highly insulating with conductivities ( ⁇ ) on the order of ⁇ 10 -9 S cm -1 for 5 nm Au nanocrystals (NCs) ( Fig. 14 ) and less than 10 -12 S cm -1 for 5.5 nm CdSe nanoparticles.
  • Replacing dodecanethiol ligands with Sn 2 S 6 4- increased the conductivity of Au NC solids by ⁇ 11 orders of magnitude approaching ⁇ ⁇ 200 S cm -1 ( Fig. 14 ). After electrical measurements the film could be easily dissolved in hydrazine or H 2 O.
  • inorganic capping agent-capping of colloidal particles is a promising approach to designing solution-processed inorganic semiconductors.
  • Figs. 13 and 36 show characteristics of a field-effect transistor with a channel assembled of 4.5 nm CdSe nanoparticles capped with Sn 2 S 6 4- and annealed for a short time at 200 °C.
  • An n-type gate effect with current modulation I on / I off ⁇ 10 5 was observed along with an electron mobility ⁇ ⁇ 3 ⁇ 10 -2 cm 2 V -1 s -1 in the saturation regime.
  • inorganic capping agent-capped CdSe NCs Compared to other CdSe nanoparticles, inorganic capping agent-capped CdSe NCs enabled appreciable performance of solid state FETs while retaining optical and electronic tunability provided by the quantum confinement. Furthermore, illumination of the inorganic capping agent-capped CdSe nanoparticles increased their conductivity by several orders of magnitude, as shown for Sn 2 Se 6 4- - capped CdSe NCs ( Fig. 13 ).
  • Close-packed films (colloidal materials) of colloidal particles can be deposited on highly doped Si wafers with 110 nm thick layer of thermal oxide and back-gate geometry by spin-coating and then aluminum electrodes are deposited on the film using a shadow mask.
  • the total amount of inorganic capping agent in the colloidal materials was less than about 10 wt% of the colloidal materials; at this weight percentage the inorganic capping agent can provide colloidal stabilization but does not form a continuous conductive matrix of phase-separated metal chalcogenide ( Fig. 38b ).
  • the deposited close-packed films can be annealed at 200 °C for about 0.5 ⁇ 1hr.
  • I D source and drain electrodes
  • V G gate terminal
  • I D increased with increasing V G , typical for n-type conductivity through FET channel ( Figs. 38c,d ).
  • the field effect mobility ( ⁇ lin ) estimated from the slope of I D vs V G plot ( Fig. 38d ) was significantly improved as 11.32 ⁇ 15.3 cm 2 /Vs and the I ON / I OFF ratio was ⁇ 1x10 3 .
  • the wave functions of the colloidal materials with physically-smaller inorganic capping agents can strongly couple and form short-range and/or long-range delocalized electronic structure.
  • the quantum mechanical coupling energy can be approximated as ⁇ ⁇ h ⁇ ⁇ exp ⁇ -2(2 m * ⁇ E / ⁇ 2 ) 1/2 ⁇ x ⁇ , where h is Planck's constant, ⁇ is the tunneling rate between two nanocrystal neighbors, m* is the carrier effective mass, ⁇ E and ⁇ x are the height of tunneling barrier and the shortest edge-to-edge distance between the nanoparticles, respectively.
  • inorganic capping agents behaved as electronically transparent "glue” for nanoparticles.
  • inorganic capping agents can also be used for creating composite materials where the properties of the inorganic capping agent and nanoparticle components complement each other.
  • Thermal decomposition of the hydrazinium-based inorganic capping agents was shown to generate various chalcogenide phases with n- and p-type conductivity, and phase-change properties.
  • combining electron-conducting nanowires e.g., CdS
  • hole-conducting hosts e.g., CuIn 1-x Ga x Se 2
  • I-V curves for each sample with gold electrodes showed high conductivity and excellent linearity over the entire range of applied voltages.
  • the measured conductivities for drop-cast films spread in a broad range from 30 to 200 S cm -1 , depending upon the concentration of cracks and other structural defects.
  • spray-coated samples on average showed higher conductivities of 200-450 S cm -1 at room temperature ( Figure 28C ).
  • Thermopower measurements revealed p-type conductivity and Seebeck coefficients of ⁇ 170-250 ⁇ V/K ( Figure 28D ). Unlike electrical conductivity which is very sensitive to homogeneity of the sample, thermopower is an inherent material property and is reproducible within ⁇ 10% for the series of same-formulated samples.
  • Representative literature examples include flash-evaporated n-type Bi-Te-based thin films ( ⁇ 540 S cm -1 ), flash-evaporated Bi 0.5 Sb 1.5 Te 3 thin films ( ⁇ 550 S cm -1 ), co-evaporated Bi 2 Te 3 thin films ( ⁇ 166 S cm -1 , 770 S cm -1 ), and sputtered Bi-Sb-Te thin films ( ⁇ 70-200 S cm -1 ).
  • formamide solutions of Cu 2 Se•Sn 2 S 6 and ZnS•Sn 2 S 6 were prepared. These solutions were admixed at an approximate 2:1 atomic ratio for Cu to Zn and the amount of Sn 2 S 6 was adjusted to an approximate 1:1 atomic ratio for Zn to Sn.
  • the deposition solution was drop-cast onto a hydrophilized glass substrate.
  • the cast colloidal material was then thermally processed at 600 °C for 2 h.
  • the powder X-ray diffraction pattern of the as-made alloy matches the diffraction pattern for CZTS (JCPDS no. 26-0575), Cu 2 ZnSnS 4 . See Fig. 41 .
  • the composition of the as-made alloy is believed to contain selenium and have the approximate formula Cu 2 ZnSn(S,Se) 4 .
  • Samples of platinum bridged CdSe•Sn 2 Se 6 and platinum bridged CdSe•Sn 2 S 6 were prepared by warming solutions of the respective colloidal particles in formamide to 80°C. To these solutions, solutions of K 2 PtCl 4 in formamide were added. From these solutions the colloidal materials Pt[CdSe•Sn 2 Se 6 ] and Pt[CdSe•Sn 2 S 6 ] precipitated. The colloidal materials were then isolated and washed with a solvent, e.g., formamide and/or water, capable of removing any free ionic species.
  • a solvent e.g., formamide and/or water
  • a hydrazine solution of In 2 Se 3 -Se (49 ⁇ L; 0.25M) was diluted with 1.5 mL N 2 H 4 in a 6 mL vial. Then 1 mL of 5mg/mL Cu 2 Se in toluene and 1 mL extra toluene were added to the vial. The two-phase mixture was vigorously stirred at room temperature for 4 hours. The upper (toluene) phase was discarded and the bottom (hydrazine) phase was washed 3 times with 2 mL toluene.
  • Example 10 Using the procedure of Example 10, a solution of CuInSe 2 •In 2 Se 4 is made from CuInSe 2 and In 2 Se 4 2- . Deposition and thermal processing of the colloidal particles yields copper indium diselenide films where mass lost during thermal processing is less than about 5%, as determined by TGA.

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Claims (12)

  1. Isolierbares kolloidales Teilchen aufweisend ein anorganisches Blockierungsmittel, das an eine Oberfläche eines Nanoteilchens gebunden vorliegt, und im Wesentlichen kein organisches Blockierungsmittel, wobei das anorganische Blockierungsmittel ein Ion aufweist ausgewählt aus der Gruppe bestehend aus As3 3-, As4 2-, As5 3-, As7 3-, As11 3-, AsS3 3-, As2Se6 3-, As2Te6 3-, As10Te3 2-, Au2Te4 2-, Au3Te4 3-, Bi3 3-, Bi4 2-, Bi5 3-, Bi7 3-, GaTe2-, Ge9 2-, Ge9 4-, Ge2S6 4-, HgSe2 2-, Hg3Se4 2-, In2Se4 2-, In2Te4 2-, Ni5Sb17 4-, Pb5 2-, Pb7 4-, Pbg 4-, Pb2Sb2 2-, Sb3 3-, Sb4 2-, Sb7 3-, SbSe4 3-, SbSe4 5-, SbTe4 5-, Sb2Se3 -, Sb2Te5 4-, Sb2Te7 4- , Sb4Te4 4-, Sb9Te6 3-, Se2 2-, Se3 2-, Se4 2-, Se5,6 2-, Se6 2-, Sn4 2-, Sn5 2-, Sn9 3-, Sn9 4-, SnS4 4-, SnSe4 4-, SnTe4 4-, SnS4Mn2 5-, Sn2S6 4-, Sn2Se6 4-, Sn2Te6 4-, Sn2Bi2 2-, Sn8Sb3-, Te2 2-, Te3 2-, Te4 2-, Tl2Te2 2-, TlSn8 3-, TlSn8 5-, TlSn9 3-, TlTe2 2-, und einer Mischung davon, oder ein lösliches Metallchalcogenid aufweisend ausgewählt aus der Gruppe bestehend aus molekularen Verbindungen, die von CulnSe2, CuInXGa1-xSe2, Ga2Se3, In2Se3, In2Te3, Sb2S3, Sb2Se3, Sb2Te3, ZnTe, und einer Mischung davon abgeleitet sind.
  2. Lösung des kolloidalen Teilchens gemäß Anspruch 1, aufweisend ein Lösungsmittel und das anorganische Blockierungsmittel, das an eine Oberfläche eines Nanoteilchens gebunden vorliegt; wobei die Lösung im Wesentlichen kein organisches Blockierungsmittel aufweist, und wobei wahlweise das Lösungsmittel im Wesentlichen kein Hydrazin aufweist.
  3. Lösung oder Teilchen nach einem der vorstehenden Ansprüche, wobei das Nanoteilchen ausgewählt ist aus einer Gruppe bestehend aus AIN, AlP, AlAs, Ag, Au, Bi, Bi2S3, Bi2Se3, Bi2Te3, CdS, CdSe, CdTe, Co, CoPt, CoPt3, Cu, Cu2S, Cu2Se, CulnSe2, CuIn(1-x)Gax(S,Se)2, Cu2ZnSn(S,Se)4, Fe, FeO, Fe2O3, Fe3O4, FePt, GaN, GaP, GaAs, GaSb, GaSe, Ge, HgS, HgSe, HgTe, InN, InP, InSb, InAs, Ni, PbS, PbSe, PbTe, Pd, Pt, Ru, Rh, Si, Sn, ZnS, ZnSe, ZnTe, Au/PbS, Au/PbSe, Au/PbTe, Ag/PbS, Ag/PbSe, Ag/PbTe, Pt/PbS, Pt/PbSe, Pt/PbTe, Au/CdS, Au/CdSe, Au/CdTe, Ag/CdS, Ag/CdSe, Ag/CdTe, Pt/CdS, Pt/CdSe, Pt/CdTe, Au/FeO, Au/Fe2O3, Au/Fe3O4, Pt/FeO, Pt/Fe2O3, Pt/Fe3O4, FePt/PbS, FePt/PbSe, FePt/PbTe, FePt/CdS, FePt/CdSe, FePt/CdTe, CdSe/CdS, CdSe/ZnS, InP/CdSe, InP/ZnS, InP/ZnSe, InAs/CdSe, InAs/ZnSe, und einer Mischung davon.
  4. Verfahren zur Herstellung des kolloidalen Teilchens gemäß Anspruch 1, aufweisend
    Zugeben einer Lösung eines wie in Anspruch 1 definierten Blockierungsmittels in ein erstes Lösungsmittel und eine Lösung eines Nanoteilchens in einem zweiten Lösungsmittel, wobei das zweite Lösungsmittel mit dem ersten Lösungsmittel erkennbar nicht vermischbar ist, wobei wahlweise
    das Nanoteilchen eine Größe und eine Form vor dem Zugeben aufweist und wobei die Größe und die Form vor dem Zugeben annähernd die gleiche ist wie eine Größe und Form nach dem Zugeben,
    das erste und zweite Lösungsmittel im Wesentlichen kein Hydrazin aufweisen, oder
    das kolloidale Teilchen im Wesentlichen kein organisches Blockierungsmittel aufweist.
  5. Verfahren zur Herstellung eines kolloidalen Materials, einer kolloidalen Matrix, oder einer Legierung, aufweisend:
    Abscheiden einer Lösung, die ein Lösungsmittel und eine erste Vielzahl kolloidaler Teilchen aufweist, auf einem Substrat; wobei ein kolloidales Teilchen eine erste Vielzahl anorganisches Blockierungsmittel aufweist, das an eine Oberfläche eines Nanoteilchens gebunden vorliegt; wobei die Lösung im Wesentlichen kein organisches Blockierungsmittel aufweist und wobei das anorganische Blockierungsmittel ein Ion aufweist ausgewählt aus der Gruppe bestehend aus As3 3-, As4 2-, As5 3-, As7 3-, As11 3-, AsS3 3-, As2Se6 3-, As2Te6 3-, As10Te3 2-, Au2Te4 2-, Au3Te4 3-, Bi3 3-, Bi4 2-, Bi5 3-, Bi7 3-, GaTe2-, Ge9 2-, Ge9 4-, Ge2S6 4-, HgSe2 2-, Hg3Se4 2-, In2Se4 2-, In2Te4 2-, Ni5Sb17 4-, Pb5 2-, Pb7 4--, Pb9 4-, Pb2Sb2 2-, Sb3 3-, Sb4 2-, Sb7 3-, SbSe4 3-, SbSe4 5-, SbTe4 5-, Sb2Se3, Sb2Te5 4-, Sb2Te7 4-, Sb4Te4 4-, Sb9Te6 3-, Se2 2-, Se3 2-, Se4 2- , Se5,6 2-, Se6 2-, Sn4 2-, Sn5 2-, Sn9 3-, Sn9 4-, SnS4 4-, SnSe4 4-, SnTe4 4-, SnS4Mn2 5-, Sn2S6 4-, Sn2Se6 4-, Sn2Te6 4-, Sn2Bi2 2-, Sn8Sb3-, Te2 2-, Te3 2-, Te4 2-, Tl2Te2 2-, TlSn8 3-, TlSn8 5-, TlSn9 3-, TlTe2 2-, und einer Mischung davon, oder ein lösliches Metallchalcogenid aufweist ausgewählt aus der Gruppe bestehend aus molekularen Verbindungen, die von CulnSe2, CuInXGa1-xSe2, Ga2Se3, In2Se3, In2Te3, Sb2S3, Sb2Se3, Sb2Te3, ZnTe, und einer Mischung davon abgeleitet sind.
  6. Verfahren gemäß Anspruch 5, wobei das kolloidale Teilchen ferner eine zweite Vielzahl anorganisches Blockierungsmittel aufweist, das an die Oberfläche des Nanoteilchens gebunden vorliegt.
  7. Verfahren nach einem der Ansprüche 5 bis 6, wobei die Lösung ferner anorganisches Blockierungsmittel aufweist, das nicht an eine Oberfläche des Nanoteilchens gebunden vorliegt.
  8. Verfahren nach einem der Ansprüche 5 bis 7, ferner aufweisend Abscheiden einer zweiten Lösung, die ein zweites Lösungsmittel und eine zweite Vielzahl kolloidaler Teilchen aufweist, auf einem Substrat; wobei ein kolloidales Teilchen der zweiten Vielzahl ein anorganisches Blockierungsmittel aufweist, das an eine Oberfläche eines Nanoteilchens gebunden vorliegt und von dem kolloidalen Teilchen der ersten Vielzahl verschieden ist; und wobei die Lösung im Wesentlichen kein organisches Blockierungsmittel aufweist.
  9. Verfahren nach einem der Ansprüche 5 bis 8, wobei die kolloidalen Teilchen ausgewählt sind aus der Gruppe bestehend aus Au•AsS3, Au•Sn2S6, Au•SnS4, Au•Sn2Se6, Au•In2Se4, Bi2S3•Sb2Te5, Bi2S3•Sb2Te7, Bi2Se3•Sb2Te5, Bi2Se3•Sb2Te7, CdSe•Sn2S6, CdSe•Sn2Te6, CdSe•In2Se4, CdSe•Ge2S6, CdSe•Ge2Se3, CdSe•HgSe2, CdSe•ZnTe, CdSe•Sb2S3, CdSe•SbSe4, CdSe•Sb2Te7, CdSe•In2Te3, CdTe•Sn2S6, CdTe•Sn2Te6, CdTe•In2Se4, Au/PbS•Sn2S6, Au/PbSe•Sn2S6, Au/PbTe•Sn2S6, Au/CdS•Sn2S6, Au/CdSe•Sn2S6, Au/CdTe•Sn2S6, FePt/PbS•Sn2S6, FePt/PbSe•Sn2S6, FePt/PbTe•Sn2S6, FePt/CdS•Sn2S6, FePt/CdSe•Sn2S6, FePt/CdTe•Sn2S6, Au/PbS•SnS4, Au/PbSe•SnS4, Au/PbTe•SnS4, Au/CdS•SnS4, Au/CdSe•SnS4, Au/CdTe•SnS4, FePt/PbS•SnS4 FePt/PbSe•SnS4, FePt/PbTe•SnS4, FePt/CdS•SnS4, FePt/CdSe•SnS4, FePt/CdTe•SnS4, Au/PbS•In2Se4 Au/PbSe•In2Se4, Au/PbTe•In2Se4, Au/CdS•In2Se4, Au/CdSe•In2Se4, Au/CdTe•In2Se4, FePt/PbS•In2Se4 FePt/PbSe•In2Se4, FePt/PbTe•In2Se4, FePt/CdS•In2Se4, FePt/CdSe•In2Se4, FePt/CdTe•In2Se4, CdSe/CdS•Sn2S6, CdSe/CdS•SnS4, CdSe/ZnS•SnS4, CdSe/CdS•Ge2S6, CdSe/CdS•In2Se4, CdSe/ZnS•In2Se4, Cu•In2Se4, Cu2Se•Sn2S6, Pd•AsS3, PbS•SnS4, PbS•Sn2S6, PbS•Sn2Se6, PbS•In2Se4, PbS•Sn2Te6, PbS•AsS3, ZnSe•Sn2S6, ZnSe•SnS4, ZnS•Sn2S6, ZnS•SnS4, und einer Mischung davon.
  10. Verfahren zur Herstellung einer kolloidalen Matrix oder einer Legierung, aufweisend:
    Abscheiden eines kolloidalen Materials auf einem Substrat; und
    Erhitzen des kolloidalen Materials; wobei das kolloidale Material im Wesentlichen kein organisches Blockierungsmittel aufweist und eine Vielzahl kolloidaler Teilchen aufweist, die anorganische Blockierungsmittel aufweisen, die an eine Oberfläche der Nanoteilchen gebunden vorliegen, wobei das anorganische Blockierungsmittel ein Ion aufweist ausgewählt aus der Gruppe bestehend aus As3 3-, As4 2-, As5 3-, As7 3-, As11 3-, AsS3 3- , As2Se6 3-, As2Te6 3-, As10Te3 2-, Au2Te4 2-, Au3Te4 3-, Bi3 3-, Bi4 2-, Bi5 3-, Bi7 3-, GaTe2-, Ge9 2-, Ge9 4-, Ge2S6 4-, HgSe2 2-, Hg3Se4 2-, In2Se4 2-, In2Te4 2-, Ni5Sb17 4-, Pb5 2-, Pb7 4--, Pb9 4-, Pb2Sb2 2-, Sb3 3-, Sb4 2-, Sb7 3-, SbSe4 3-, SbSe4 5-, SbTe4 5-, Sb2Se3 -, Sb2Te5 4-, Sb2Te7 4-, Sb4Te4 4-, Sb9Te6 3- , Se2 2-, Se3 2-, Se4 2-, Se5,6 2-, Se6 2-, Sn4 2-, Sn5 2-, Sn9 3-, Sn9 4-, SnS4 4-, SnSe4 4-, SnTe4 4-, SnS4Mn2 5-, Sn2S6 4-, Sn2Se6 4-, Sn2Te6 4-, Sn2Bi2 2-, Sn8Sb3-, Te2 2-, Te3 2-, Te4 2-, Tl2Te2 2-, TlSn8 3- , TlSn8 5-, TlSn9 3-, TlTe2 2-, und einer Mischung davon, oder ein lösliches Metallchalcogenid aufweist ausgewähl aus der Gruppe bestehend aus molekularen Verbindungen, die von CulnSe2, CuInXGa1-xSe2, Ga2Se3, In2Se3, In2Te3, Sb2S3, Sb2Se3, Sb2Te3, ZnTe, und einer Mischung davon, abgeleitet sind.
  11. Vorrichtung aufweisend das kolloidale Material, die kolloidale Matrix, oder Legierung, die durch das Verfahren nach einem der Ansprüche 5 bis 10 hergestellt sind.
  12. Vorrichtung gemäß Anspruch 11, wobei die Vorrichtung ausgewählt ist aus der Gruppe bestehend aus einer gedruckten Schaltung, einer photovoltaischen Zelle, einer piezoelektrischen Zelle, einer thermoelektrischen Schicht, einer optoelektronischen Schicht, einer lichtemittierenden Diode, einer ferroelektrischen Schicht, eines Dünnfilmtransistors, einer Floating Gate Speichervorrichtung, einer Phasenänderungsschicht, Licht-, Röntgen- oder Gamma-Strahlungs-Detektor, einer Sensorvorrichtung, einer Abbildungsvorrichtung, und einer Mischung davon.
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